EP0671158A1 - Permanent wave process for keratinic fibres - Google Patents

Abstract

The invention relates to a new process for treating keratin materials, in particular hair, with a view to obtaining permanent deformation of the latter, in particular in the form of permed hair, said process being characterized in that it comprises the following steps: (i) a composition containing thioglycolic acid and / or thiolactic acid and / or mercaptopropionic acid and / or one of their salts and / or one is applied to the keratin material to be treated of their esters, the means (rollers) necessary for the mechanical tensioning of the keratin material being used before, during or after said application, (ii) optionally, the keratin material thus treated is then subjected to a heat treatment ( heating), (iii) then the keratin material thus treated is rinsed, (iv) the keratin material thus rinsed is then left to stand, (v) and finally the kera material is separated and thus rested the tensioning means used in step (i). The method according to the invention makes it possible, among other advantages, to dispense with the use of oxidizing agents (fixing).

Description

The present invention relates to a new process for treating keratin materials, in particular the hair, with a view to obtaining permanent deformation of the latter, in particular in the form of permed hair, said process being particularly usable in the field of hair salons. hairdressing, beauty, cosmetics and the like, professionals.

It is known that the most usual technique for obtaining permanent deformation of the hair consists, firstly, in opening the disulfide bonds -SS- of keratin (cystine) using a composition containing an agent reducing agent (reduction step) then, after having preferably rinsed the hair thus treated, in reconstituting said disulphide bonds in a second step by applying, to the hair previously tensioned (curlers and others), an oxidizing composition (step oxidation, also called fixation) so as to finally give the hair the desired shape. This technique thus makes it possible to carry out either the waving of the hair, or their straightening or their straightening. The new form imposed on the hair by a chemical treatment such as above is eminently durable over time and resists in particular the action of washing with water or with shampoos, and this in contrast to the simple conventional techniques of temporary deformation, such as styling.

The reducing compositions which can be used for carrying out the first step of a perming operation generally contain, as reducing agents, sulfites, bisulfites or thiols. Among the latter, mention may be made of cysteine and its various derivatives, cysteamine and its derivatives, thiolactic acid, thioglycolic acid and its esters, in particular glycerol monothioglycolate, and thioglycerol. In this respect, and although having an unpleasant odor, thioglycolic acid is particularly effective, and thus constitutes the reference compound permanently for reducing the disulfide bonds of keratin; cysteine, on the other hand, produces a much weaker odor than that of thioglycolic acid or glycerol monothioglycolate, but the degree of crimp obtained is unfortunately lower and far from being completely satisfactory.

As regards the oxidizing compositions necessary for carrying out the fixing step, in practice, use is most often made of compositions based on hydrogen peroxide. However, it turns out that the use of hydrogen peroxide has the particular drawback of leading to a more or less marked degradation of the original color of the hair.

In addition, and in particular in the case where the reducing agent used is thioglycolic acid, it is observed that the succession of reduction-oxidation cycles (ie perming operations) on the hair leads, in a harmful way, to a progressive degradation not only of the color of the latter (discoloration) but also of its mechanical behavior (reduction of the breaking energy) in particular due a significant increase in the level of keratocysteic acid in the treated hair.

The present invention aims in particular to solve the above problems.

More specifically, the present invention aims to propose a new treatment process suitable for the permanent deformation of keratin materials and which makes it possible to dispense with the implementation of the conventional steps of fixing by powerful oxidizing agents.

It also aims to propose a method as above which also makes it possible to obtain high quality crimps.

It also aims to propose a method as above which makes it possible to limit, or even eliminate, the mechanical degradation of the hair, after repetition of the treatment.

It also aims to propose a method as above, limiting, even eliminating, the discoloration of the hair.

Finally, it aims to propose a process as above which is, overall, slightly odorous on the one hand, and slightly irritating to the skin and / or the scalp on the other hand.

However, it has been found by the applicant that these aims, and others, can be successfully achieved by carrying out a suitable selection of the composition known as starting reducing agent associated with a particular operating mode for using this composition. This discovery is the basis of the present invention.

• (i) on applique sur la matière kératinique à traiter une composition contenant de l'acide thioglycolique et/ou de l'acide thiolactique et/ou de l'acide mercaptopropionique et/ou un de leurs sels et/ou un de leurs esters, les moyens (tels que par exemple rouleaux, bigoudis et analogues) nécessaires à la mise sous tension mécanique de la matière kératinique étant mis en oeuvre avant, pendant ou après ladite application,
• (ii) éventuellement, on soumet ensuite la matière kératinique ainsi traitée à un traitement thermique,
• (iii) puis on rince la matière kératinique ainsi traitée,
• (iv) on laisse ensuite reposer la matière kératinique ainsi rincée,
• (v) et enfin on sépare la matière kératinique ainsi reposée des moyens (rouleaux et autres) de mise sous tension utilisés à l'étape (i).

Thus, a new treatment process is now proposed according to the present invention suitable for deformation and / or shaping, and this permanently, of keratin materials, and in particular of the hair, said process being characterized by the fact that it includes the following stages:

• (i) a composition containing thioglycolic acid and / or thiolactic acid and / or mercaptopropionic acid and / or one of their salts and / or one of their esters is applied to the keratin material to be treated the means (such as for example rollers, curlers and the like) necessary for the mechanical tensioning of the keratin material being used before, during or after said application,
• (ii) optionally, the keratinous material thus treated is then subjected to a heat treatment,
• (iii) then the keratinous material thus treated is rinsed,
• (iv) the keratinous material thus rinsed is then left to stand,
• (V) and finally the keratinous material thus rested is separated from the tensioning means (rollers and the like) used in step (i).

The method according to the invention is particularly suitable for obtaining permed hair.

Applied to healthy hair, and even repeated several times, the method according to the invention has the main advantages, inter alia, of driving, and this without releasing unpleasant odors on the one hand and in a non-irritating manner for the skin and / or scalp, on the other hand, to hair that is not bleached or substantially not bleached, mechanically resistant, and having fine curls.

However, other characteristics, aspects and advantages of the invention will appear even more clearly on reading the detailed description which follows, as well as the various concrete examples, but in no way limiting, intended to illustrate it.

Although the description which follows essentially revolves around the particular case of hair treatment, it will be noted here that the method according to the invention is applicable to any keratin material in general, in particular eyelashes, whiskers, hair, wool and others.

l'acide 3-mercaptopropionique, de formule (3) :

        HS-CH₂-CH₂-COOH   (3)


ou un de leurs sels ou un de leurs esters.The reducing agents used in the context of the process according to the invention are thioglycolic acid, of formula (1):

HS-CH₂-COOH (1)


thiolactic acid, of formula (2):

3-mercaptopropionic acid, of formula (3):

HS-CH₂-CH₂-COOH (3)


or one of their salts or one of their esters.

Among the cosmetically acceptable salts of the products (1), (2) and (3) above, there may be mentioned more particularly the ammonium salts, the primary, secondary or tertiary amine salts, the alkali metal salts earthy. As primary, secondary or tertiary amine salts, mention may be made, respectively, of monoethanolamine, di-isopropanolamine and triethanolamine.

Among the esters of compounds (1), (2) and (3) above, there may be mentioned glycerol monothioglycolate, ethylene glycol monothioglycolate, the azeotropic mixture of hydroxy-2-propyl thioglycolate and of thioglycolate of 1-hydroxy-methyl-1-ethyl described in patent application FR-A-2 679 448, glycerol monothiolactate, ethylene glycol monothiolactate, glycerol 3-mercaptopropionate, ethylene 3-mercaptopropionate glycol.

These reducing agents are generally used in cosmetically acceptable compositions, which are moreover already well known per se in the existing state of the art of crimping formulations intended to carry out the first step (reduction) of a perm operation. . Thus, as usual and conventional additives, which can be used alone or in mixtures, mention may more particularly be made of surfactants of nonionic, anionic, cationic or amphoteric type and among these, mention may be made of alkylsulphates, alkylbenzenesulphates , alkyl ether sulfates, alkyl sulfonates, quaternary ammonium salts, alkyl betaines, oxyethylenated alkylphenols, alkanolamides of fatty acids, esters of oxyethylenated fatty acids as well as other nonionic surfactants of the hydroxypropylether type.

When the reducing composition contains at least one surfactant, this is generally present at a maximum concentration of 30% by weight, and preferably between 0.5 and 10% by weight, relative to the total weight of the reducing composition .

In order to improve the cosmetic properties of the hair or to attenuate or avoid its degradation, the reducing composition may also contain a treating agent of cationic, anionic, nonionic or amphoteric nature.

Among the particularly preferred treating agents, mention may in particular be made of those described in French patent applications Nos. 2,598,613 and 2,470,596. It is also possible to use, as treating agents, volatile or non-linear or cyclic silicones and their mixtures, the polydimethylsiloxanes, quaternized polyorganosiloxanes such as those described in French patent application No. 2,535,730, polyorganosiloxanes with aminoalkyl groups modified by alkoxycarbonyalkyl groups such as those described in US patent No. 4,749,732, polyorganosiloxanes such as polydimethylsiloxane-polyoxyalkyl copolymer of the dimethicone copolyol type, a polydimethylsiloxane with stearoxy- (stearoximethicone) groupings, a polydimethylsiloxane-dialkylammonium acetate copolymer or a polydimethyl-siloxane polyalkylbetaine copolymer described in the patent application No. 2,197,352, organo-polysiloxanes modified with mercapto or mercaptoalkyl groups such as those described in French patent No. 1,530,369 and in European patent application No. 295,780, as well as silanes such as stearoxytrimethylsilane .

The reducing composition may also contain other treating ingredients such as cationic polymers such as those used in the compositions of French patents No. 79.32078 (FR-A- 2 472 382) and 80.26421 (FR-A- 2 495 931), or alternatively cationic polymers of the ionene type such as those used in the compositions of Luxembourg patent n ° 83703, basic amino acids (such as lysine, arginine) or acids (such as glutamic acid, aspartic acid) , peptides and their derivatives, protein hydrolysates, waxes, bulking and penetrating agents or making it possible to reinforce the effectiveness of the reducing agent such as the SiO2 / PDMS (polydimethylsiloxane) mixture, dimethylisosorbitol, urea and its derivatives, pyrrolidone, N-alkyl-pyrrolidones, thiomorpholinone, alkyl ethers of alkylene glycol or dialkylene glycol such as for example propylene glycol monomethyl ether, dipr monomethyl ether opylene glycol, monoethylene ether of ethylene glycol and monoethyl ether of diethylene glycol, C₃-C₆ alkanediols such as, for example, 1,2-propanediol and 1,2-butanediol, 2-imidazolidinone as well as other compounds such as fatty alcohols, lanolin derivatives, active ingredients such as panthothenic acid, hair loss agents, dandruff agents, thickeners, suspending agents, sequestering agents, clouding agents, colorants, sun filters as well as perfumes and preservatives.

When thioglycolic acid or thiolactic acid or 3-mercaptopropionic acid, or one of their salts, is used as reducing agent, the pH of the whole of the reducing composition is preferably between 6.5 and 11.5 and even more preferably between 7 and 10.

When the esters of thioglycolic acid or of thiolactic acid or of 3-mercaptopropionic acid are used as reducing agent, the pH of the whole of the reducing composition is preferably between 5 and 11 and even more preferably between 6 and 10.

These pHs can be obtained and / or conventionally adjusted by adding either basifying agents, such as, for example, ammonia, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, di-isopropanolamine, 1,3-propane diamine , an alkali or ammonium carbonate or bicarbonate, an organic carbonate such as guanidine carbonate, or alternatively an alkali hydroxide, all these compounds can of course be taken alone or as a mixture, either of acidifying agents such as for example hydrochloric acid, acetic acid, lactic acid or boric acid.

In the permanent reducing compositions which can be used in the context of the invention, the reducing agents mentioned above are generally present at a concentration which can be between 1 and 30% by weight, and preferably between 3 and 20% by weight relative to the total weight of the reducing composition.

The reducing composition may be in the form of a lotion, thickened or not, a cream, a gel, or any other suitable form.

The reducing composition can also be of the exothermic type, that is to say causing a certain heating during application to the hair, which brings pleasure to the person who undergoes the perm or straightening.

The reducing composition can also contain a solvent such as for example ethanol, propanol, or isopropanol or also glycerol at a maximum concentration of 20% relative to the total weight of the composition.

The vehicle for the compositions is preferably water or an aqueous-alcoholic solution of a lower alcohol such as ethanol, isopropanol or butanol.

When the compositions are intended for a hair straightening or straightening operation, the reducing composition is preferably in the form of a thickened cream so as to keep the hair as straight as possible. These creams are produced in the form of "heavy" emulsions, for example based on glyceryl stearate, glycol stearate, self-emulsifying waxes, fatty alcohols, etc.

It is also possible to use liquids or gels containing thickening agents such as carboxyvinyl polymers or copolymers which "stick" the hair and keep it in the straightened position during the setting time.

Finally, the compositions can also be in so-called "self-neutralizing" or even "self-regulated" form and in this case, the reducing agents of general formula (1) and (2) are associated with at least one disulfide known for its use in a reducing composition for self-neutralizing perm.

Among such known disulfides, mention may in particular be made of dithioglycolic acid, dithioglycerol, cystamine, N, N'-diacetyl-cystamine, cystine, pantethine, and the disulphides of N- (mercapto-alkyl) ω- hydroxyalkylamides described in patent application EP-A-354,835, the disulphides of N-mono or N, N-dialkylmercapto-4 butyramides described in patent application EP-A-368,763, the disulphides of aminomercapto-alkylamides described in patent application EP-A-432,000, the disulphides of derivatives of N- (mercaptoalkyl) -succinamic acids or of N- (mercaptoalkyl) -succinimides described in patent application EP-A-465,342, and the disulphides of alkylaminomercaptoalkylamides described in patent application EP-A-514 282. These disulfides are generally present in a molar ratio of 0.5 to 2.5, and preferably 1 to 2, relative to the reducing agent (see patent US 3,768,490).

In accordance with the first step of the process according to the present invention (step (i)), the compositions containing the reducing agent (s) of formulas (1), (2) or (3) given above, or one of their salts or one of their esters is then applied to the hair to be treated, which will preferably have been previously wet.
This application can be carried out before, during or after the usual step of tensioning the hair in a form corresponding to the final shape desired for the latter (curls for example), this step being itself capable of being implemented by any means, mechanical in particular, suitable and known per se for keeping hair under tension, such as, for example, rollers, curlers and the like.

According to an optional step of the process of the invention (step (ii)), it is possible, after application of the reducing composition, to subject the hair to a heat treatment, that is to say heating. In this case, the heating temperature is generally between 30 and 60 ° C. Although not compulsory, this heating is nevertheless preferred, because it allows the final degree of hair crimp to be adjusted as desired. Of course, work at room temperature is possible, and is therefore not excluded from the scope of the invention. In practice, this operation can be carried out using a hairdressing helmet, a hair dryer, an infrared ray dispenser, or any other conventional heating appliance.

Before proceeding to the next rinsing step, it is conventionally advisable to allow the hair to which the reducing composition has been applied to stand for a few minutes, generally between 2 and 30 minutes, preferably between 5 and 20 minutes. , and this so as to give the reducer time to act correctly on the hair; during this waiting phase, which includes the optional heating step mentioned above, care is taken that the hair does not dry completely and thus remains moist until the next step is carried out (use caps, protective gels for example).

In a third essential step of the process according to the invention (step (iii)), the hair impregnated with a reducing composition is then rinsed thoroughly, generally with water.

According to a fourth absolutely essential step of the treatment method according to the invention (step (iv)), the hair thus rinsed is then left in a rest or waiting phase. If we omit this step, it is not possible to obtain correct crimping. According to the invention, this rest (or waiting) phase of the rinsed hair can last between 3 and 60 min, and it is preferably between 5 and 30 min. It is generally carried out by leaving the wet hair from the rinsing to stand in the open air (room temperature). A waiting phase conducted at a higher temperature is not excluded, and is also suitable. Note that this step can be carried out until perfectly dry hair is obtained, the method according to the invention in this case being similar (except in terms of result) to the so-called "styling" procedures.

Finally, in the last step of the method according to the invention (step (v)), mechanical means (rollers, curlers and the like) are removed from the hair which kept the hair under tension and in the desired shape throughout the treatment. , whereby one can finally obtain a hair having for example beautiful permanent curls (in particular water resistant), and this without having to implement a chemical fixing step (oxidation).

Except for the particular case of the “styling” type process mentioned above, it will be noted that, before or after the implementation of step (v) above (removal of the mechanical means for tensioning the hair) , it is possible to implement a new step of rinsing with hair water. When the removal of the rollers is carried out on already perfectly dry hair, the implementation of a new rinsing step proves to be important if one wishes to obtain a fine crimp.

In the process according to the invention, when the reducing composition contains thioglycolic acid, thiolactic acid or mercaptopropionic acid or their salts at a concentration greater than 8% by weight relative to the total weight of the composition , the pH of the reducing composition is preferably less than 9 and the waiting phase is less than 7 minutes.

Concrete examples illustrating the invention will now be given. For the purpose of a significant comparison, the same starting hair (before treatment) was used for all the examples.

Example 1 (invention)

• acide thioglycolique   3, 6 g
• monoéthanolamine   qs   pH 9,5
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• thioglycolic acid 3, 6 g
• monoethanolamine qs pH 9.5
• demineralized water qs 100 g

The procedure is as follows: the above reducing composition is applied to coiled and damp hair (diameter of the rollers: 9 mm); then a plastic cap is placed on the hair (which makes it possible to avoid drying the hair during the next heating step) which is then installed under an infrared dispenser (40 ° C.) for 15 minutes; then remove the cap and rinse thoroughly and thoroughly with water; the hair is then left to stand on the rollers for 15 minutes; then the rollers are removed (unwinding); finally, rinse again with water.

A wick with a fine crimp is thus finally obtained.

Example 2 (invention)

• acide thioglycolique   9,1 g
• monoéthanolamine   4 g
• bicarbonate d'ammonium   2 g
• ammoniaque   qs   pH 8,5
• eau déminéralisée   qsp   100 g

A reducing composition having the following characteristics is used:

• thioglycolic acid 9.1 g
• monoethanolamine 4 g
• ammonium bicarbonate 2 g
• ammonia qs pH 8.5
• demineralized water qs 100 g

The procedure is that of Example 1.

We get a wick with a nice crimp.

Example 3 (invention)

• acide thioglycolique   9, 1 g
• monoéthanolamine   qs   pH 9,5
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• thioglycolic acid 9, 1 g
• monoethanolamine qs pH 9.5
• demineralized water qs 100 g

The procedure is that of Example 1, except that the pause times of the two stages are limited to 5 minutes per stage.

We get a wick with a nice crimp.

Example 4 (invention)

• acide thioglycolique   9,1 g
• monoéthanolamine   qs   pH 7
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• thioglycolic acid 9.1 g
• monoethanolamine qs pH 7
• demineralized water qs 100 g

The procedure is that of Example 1.

We get a wick with a nice crimp.

Example 5 (invention)

• monothioglycolate de glycérol en solution à 68 % en poids dans le glycérol   17 g MA
• monoéthanolamine   qs   pH 9
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• glycerol monothioglycolate in 68% by weight solution in glycerol 17 g MA
• monoethanolamine qs pH 9
• demineralized water qs 100 g

The procedure is that of Example 1.

We get a wick with a nice crimp.

Example 6 (invention)

• mélange azéotrope de thioglycolate d'hydroxy-2 propyle et de thioglycolate d'hydroxy-2 méthyl-1 éthyle décrit à l'exemple 1 de FR-A-2 679 448   15 g
• monoéthanolamine   qs   pH 8
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• azeotropic mixture of 2-hydroxypropyl thioglycolate and 2-hydroxyethyl 1-methyl thioglycolate described in Example 1 of FR-A-2 679 448 15 g
• monoethanolamine qs pH 8
• demineralized water qs 100 g

The procedure is that of Example 1.

We get a wick with a nice crimp.

Example 7 (invention)

• acide mercaptopropionique   10 g
• monoéthanolamine   3 g
• carbonate de guanidine   1, 5 g
• ammoniaque   qs   pH 9
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• mercaptopropionic acid 10 g
• monoethanolamine 3 g
• guanidine carbonate 1.5 g
• ammonia qs pH 9
• demineralized water qs 100 g

The procedure is that of Example 1.

We finally get a wick with a nice crimp.

Example 8 (invention)

• acide thiolactique   11 g
• ammoniaque   3 g
• monoéthanolamine   qs   pH 8
• eau déminéralisée   qsp   100 g

A reducing composition is used having the following characteristics:

• thiolactic acid 11 g
• ammonia 3 g
• monoethanolamine qs pH 8
• demineralized water qs 100 g

The procedure is that of Example 1.

We finally get a wick with a nice crimp.

Claims (22)

1- Treatment process for the permanent deformation of keratin materials, characterized in that it comprises the following stages: (i) a composition containing thioglycolic acid and / or thiolactic acid and / or mercaptopropionic acid and / or one of their salts and / or one of their esters is applied to the keratin material to be treated the means necessary for the mechanical tensioning of the keratin material being implemented before, during or after said application, (ii) optionally, the keratinous material thus treated is then subjected to a heat treatment, (iii) then the keratinous material thus treated is rinsed, (iv) the keratinous material thus rinsed is then left to stand, (v) and finally the keratinous material thus rested is separated from the tensioning means used in step (i). 2- A method according to claim 1, characterized in that thioglycolic acid or thiolactic acid or mercaptopropionic acid or a salt thereof is used, the pH of said composition then being between 6 and 11 , 5. 3- A method according to claim 2, characterized in that said pH is between 7 and 10. 4- A method according to claim 1, characterized in that an ester of thioglycolic acid or thiolactic acid or 3-mercaptopropionic acid is used, the pH of said composition then being between 5 and 11 . 5- Method according to claim 4, characterized in that said pH is between 6 and 10. 6- A method according to any one of the preceding claims, characterized in that said salts are chosen, alone or in mixtures, from ammonium salts, secondary or tertiary amine salts, alkaline earth salts. 7- Method according to any one of the preceding claims, characterized in that said thioglycolic acid and / or said thiolactic acid and / or said mercaptopropionic acid and / or their salts and / or their said esters are present in said composition in a content ranging from 1 to 30% by weight. 8- A method according to claim 7, characterized in that said content is between 3 and 20% by weight. 9- Method according to any one of the preceding claims, characterized in that said composition contains adjuvants intended to make it cosmetically acceptable. 10- A method according to claim 9, characterized in that said adjuvants are chosen, alone or as a mixture, from surfactants of nonionic, anionic, cationic or amphoteric type, treating agents, active ingredients, agents fall arresters, anti-dandruff agents, thickeners, suspending agents, sequestering agents, clouding agents, colorants, sunscreens, perfumes and preservatives. 11- Method according to any one of the preceding claims, characterized in that said composition is in the form of a lotion, thickened or not, a cream or a gel. 12- Method according to any one of the preceding claims, characterized in that, before said application of said composition, the keratinous material is humidified. 13- Method according to any one of the preceding claims, characterized in that said heat treatment (step (ii)) is carried out at a temperature between 30 and 60 ° C. 14- Method according to any one of the preceding claims, characterized in that, before rinsing (step (iii)), the keratin material from step (i) is left to stand (waiting phase), this waiting phase including the possible step (ii). 15- Method according to claim 14, characterized in that said waiting phase lasts between 2 and 30 min, preferably between 5 and 20 min. 16- Method according to any one of the preceding claims, characterized in that the rest phase of step (iv) is carried out under heating. 17- Method according to any one of the preceding claims, characterized in that the rest phase of step (iv) lasts between 3 and 60 min. 18 - Method according to claim 17, characterized in that said rest phase of step (iv) lasts between 5 and 30 min. 19 - Method according to any one of the preceding claims, characterized in that step (iv) is carried out until total drying of the keratinous material. 20- A method according to any one of claims 1 to 18, characterized in that a new rinsing operation is carried out at the end of step (iv) or step (v). 21- Method according to claim 19, characterized in that a new rinsing operation is carried out at the end of step (v). 22- Method according to any one of the preceding claims, characterized in that said keratin material consists of hair.